Process for the control of weeds

ABSTRACT

Undesired plant growth in cultivations of useful plants which are resistant to phopho-herbicides, may be controlled with herbicidal compositions, which contain, in addition to the usual inert formulation assistants, a phospho-herbicide and a synergistic amount of at least one further herbicide selected from the group comprising prosulfuron, primisulfuron, dicamba, pyridate, dimethenamide and its S-enantiomer, metolachlor and its S-enantiomer, fluometuron, propaquizafop, atrazine, clodinafop, norflurazone, ametryn, terbutylazine, simazine, prometryn, NOA-402989, as well as the compounds of formulae.

The present invention relates to a new process for the control of weedsin useful plant cultivations, for example in the cultivation of maize,soya, cotton, rape, beet and sugar cane, which are resistant tophospho-herbicides.

The phospho-herbicides glufosinate and glyphosate are described forexample in The Pesticide Manual, Tenth Edition, 1994, Crop ProtectionPublications, BCPC. In addition, the following herbicides are similarlyknown: prosulfuron, primisulfuron, dicamba, pyridate, dimethenamide,metolachlor, fluometuron, propaquizafop, atrazine, ametryn,terbutylazine, simazine, clodinafop, norflurazone, as well as prometryn.The S-enantiomer of metolachlor is known from U.S. Pat. No. 5,002,606;the S-enantiomer of dimethenamide from U.S. Pat. No. 5,457,985. Themetabolite NOA-402989 is known from the Zeitschrift fürPflanzenkrankheiten und Pflanzenschutz, Sonderheft X, 355-360 (1984) as3-phenyl-4-hydroxy-6-chloropyridazine. The compound of formula

is described for example in U.S. Pat. No. 4,671,819; U.S. Pat. No.5,183,492 discloses the compound of formula

and the compound of formula

is known from EP-A-496 701.

It has now surprisingly been found that a quantitatively variablecombination of phospho-herbicides selected from the group comprisingglufosinate and glyphosate with at least one of the above-listed otherherbicides exhibits a synergistic effect which is capable of controllingthe majority of weeds occurring preferably in useful plant cultivationsthat are resistant to glufosinate or glyphosate, both in pre-emergenceand in post-emergence, without significantly damaging the useful plants.

Therefore, according to the present invention, a new process is proposedfor the control of weeds in the cultivation of useful plants that areresistant to phospho-herbicides, the process being characterised in thata herbicidally effective amount of a composition containing, in additionto the usual inert formulation assistants, a phospho-herbicide selectedfrom the group comprising glufosinate and glyphosate, a synergisticamount of at least one further herbicide selected from the groupcomprising prosulfuron, primisulfuron, dicamba, pyridate, dimethenamideand its S-enantiomer, metolachlor and its S-enantiomer, fluometuron,propaquizafop, atrazine, clodinafop, norflurazone, ametryn,terbutylazine, simazine, prometryn, NOA-402989, as well as the compoundsof formulae

is allowed to take effect on the cultivated plant or its habitat, withthe provision that compositions containing glufosinate and metolachlor,glufosinate and atrazine, glufosinate and metolachlor and atrazine, aswell as glufosinate and atrazine and dicamba are not used inglufosinate-resistant maize, and further that compositions containingglyphosate and atrazine are not used in glyphosate-resistant maize, andcompositions containing glyphosate and metolachlor or glyphosate anddimethenamide are not used in glyphosate-resistant soya.

It is highly surprising that the combination of a phospho-herbicide suchas glufosinate or glyphosate with at least one of the above-mentionedfurther herbicides surpasses the additional effect to be expected inprinciple on the weeds to be controlled, and thus extends the limits ofactivity of both active ingredients in particular in two differentrespects.

On the one hand, the application amounts of the individual compoundsapplied are reduced, whilst maintaining a good level of activity. On theother hand, the composition used according to the invention stillachieves a high rate of weed control where the individual substanceshave become no longer agronomically useful in small application amounts.The consequence of this is a considerable widening of the weed spectrumand an additional increase in selectivity for useful plant cultivations,which is necessary and desired in the case of an unintentional overdoseof active ingredient. In addition, the composition according to theinvention allows greater flexibility of subsequent cultivations whilstmaintaining the outstanding control of weeds in useful plants.

The herbicide mixture used according to the invention may be used onglufosinate- or glyphosate-resistant useful plants, especially maize,cotton, rape, sugar beet, sugar cane and soya, against a large number ofagronomically important weeds, such as Stellaria, Nasturtium, Agrostis,Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Phaseolus,Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus,Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium,Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola andVeronica. It may also be used for non-selective weed control and for allapplication methods that are usual in agriculture, e.g. pre-emergentapplication, post-emergent application and seed disinfecting.

Useful plant cultivations which are tolerant towards the herbicideglufosinate or glyphosate are preferably produced with the assistance ofbiotechnological methods. The assistance of biotechnological processescan be restricted to the usage of cell-biological selection processes,which are carried out in such cases preferably on cell or calluscultures that are capable of regeneration, so as to finally developglufosinate- or glyphosate-tolerant plants. However, since preciseknowledge is available about the mechanism of activity of theseherbicides, gene technology may also be employed.

Resistance towards glufosinate may be essentially attained by twodifferent experimental set-ups. On the one hand, the herbicide targetwhich in the case of glufosinate is represented by the enzyme glutaminesynthetase may be selected as the point of attack for the development ofresistance. On the other hand, the herbicidally active substance itselfmay serve as the starting point for the development of resistance. Forexample, glufosinate tolerance may be effected through the transgenicexpression of an enzyme which converts glufosinate into aphysiologically inactive form.

The first set-up makes use of the knowledge of the site of action or thepoint of attack of glufosinate, namely the enzyme glutamine synthetase.The desired tolerance may thus be effected by over-expression of theenzyme in plants or preferably by transgenic expression of variants ofthe enzyme which are tolerant to the effect of glufosinate.

Glufosinate-tolerant plants are thus produced e.g. by amplifying theherbicide target in the plant. Such gene amplification is achieved forexample by exposing plant cell cultures to selection pressure, andfurther cultivating the resistant variants or strains obtainable in thisway and regenerating them into whole plants. The said resistant cellstrains may also be fused with an appropriate receptor cell line in themanner of a protoplast fusion, and regenerated into whole plants.Alternatively, the desired gene amplification may also be attained withthe assistance of genetic engineering, whereby the number of wild typegenes in the plant genome of sensitive plants is increased by insertingfurther wild type gene replications. The source of wild type genes whichencode the enzyme glutamine synthetase may be both procaryotes andespecially eucaryotes. The eucaryotes are presented in particular byplant sources, e.g. various species of potato (Solanum tuberosum),tomato (Lycopersicon esculentum), pepper (Capsicum annumm), tobacco(Nicotiana tabacum), brassica, especially Brassica napus, variousleguminosae e.g. alfalfa (Medicago sativa), clover (Trifolium sp.), soya(Glycine max), various species of bean (Phaseolus sp., Vici sp, Vignasp.), peas (Pisum sativum), various root crops, e.g. Beta vulgaris,carrots (Daucus carota), sweet potatoes (Ipomoea batatus) as well asothers, for example Arabidopsis thaliana.

Glufosinate-tolerant plants may also be produced by inserting genes thatencode a mutated glutamine synthetase enzyme which is resistant towardsthe inhibitory activity of glufosinate. As in the case of theabove-mentioned wild type genes, these are cloned into expressioncassettes developed especially for plants, and are transformed into thedesired host plant. Appropriate expression signals (essentially promoterand termination signals, as well as signal and enhancer sequences),which are recognised by the plant cell and lead to effective expressionof the respective gene products in the transformed plant, and which maybe employed within the said expression cassettes, are most familiar tothe person skilled in the art.

The processes for the production of such glufosinate-tolerant plants aredescribed in detail in international applications having publicationnos. WO 86/02097 and WO 87/05627, and reference thereto is incorporatedin the present application.

The recombinant DNA molecules thus produced may be inserted into theplant by means of various transformation processes known to the personskilled in the art, and brought to expression there. The person skilledin the art is aware that the choice of an appropriate method isdependent in particular on the species of plant respectively selected.Suitable transformation processes include for example micro-injection(Crossway et al., Bio Techniques 4:320-334 (1986)), electroporation(Riggs et al, Proc. Natl. Acad. Sci. USA 83:5602-5606 (1986),Agrobacterium-mediated transformation (Hinchee et al., Biotechnology6:915-921 (1988)), direct gene transfer processes (Paszkowski et al.,EMBO J. 3:2717-2722 (1984)), as well as ballistic processes usingmicro-projectiles (‘ballistic particle acceleration’) [see for exampleSanford et al., U.S. Pat. No. 4,945,050; and McCabe et al.,Biotechnology 6:923-926 (1988)].

One especially preferred process for inserting recombinant DNA moleculesinto maize plants is described in the international application havingpublication no. WO 93/07278 and EP-A 0 292 435, and reference thereto isincorporated in the present application.

As has already been mentioned, glufosinate-tolerant plants may also beproduced by aiming at the herbicidally active compound as such andinactivating it. Thus, for example, genes may be isolated from thestreptomycetes strains S. hygrocopicus and S. viridochromogenes, whichwere selected for bialaphos or phosphinotricine (=glufosinate)resistance, and these genes encode an enzyme which acetylates the freeNH₂ group of glufosinate and thus transforms it to a non-herbicidallyactive compound. The transgenic expression of these phosphinothricineacetyl-transferase genes in useful plants is capable of eliminating thelocking-up of the nitrogen metabolism in the plant by the glufosinateand leads to glufosinate tolerance of said plants.

The efficiency of expression of recombinant DNA molecules of bacterialorigin in plants may be controlled by the production of synthetic genes.For example, genes of streptomycetes normally possess a very high G/Cproportion of up to 70%, which may be reduced to the usual amount forplant genes of ca. 50% by resynthesis of the gene, whilst taking intoaccount the usual codon usage of plants.

The efficiency of expression may normally be further increased byoptimising the codon usage in such a way that only those codons that aremost preferred in the respective target plant, for example maize, areused for gene resynthesis. Further details relating to the constructionof synthetic genes which have been optimised for expression in maize maybe found e.g. in the international application having publication no. WO93/07278.

The glufosinate-tolerant plants obtainable in this way may then bepropagated, i.e. produced, by means of conventional cultivation methods,whereby the glufosinate tolerance is passed on to subsequent generationsby transmission.

The processes for the production of such glufosinate-tolerant plants aredescribed in detail in the European applications having the publicationnos. EP-A 242 236, EP-A 242 246, EP-A 257 542 and EP-A 275 957 andreference thereto is incorporated in the present application.

Glyphosate-resistant plants may be produced in a similar manner, wherebya gene is used which codes for a glyphosate-tolerant EPSP synthase, asis described in EP-A-115673 and EP-A-409815.

By the expression plants or useful plant cultivations that are resistantto the herbicide glufosinate or glyphosate, as is employed in thepresent application, are understood also plants or useful plantcultivations which are resistant to those herbicides that aremetabolised in the plant or in the useful plant cultivations toglufosinate, as is the case for example when using bilanafos, or toglyphosate.

Maize which is resistant to glufosinate was treated with a tank mixturecontaining glufosinate and atrazine according to Res. Rep. North Cent.Weed Sci. Soc., 51, 169-170, 1994. Further tank mixtures for use inglufosinate-resistant maize are described in Res. Rep. Expert Comm.Weeds East Can., 1, 242-243, 1995 and Res. Rep. Expert Comm. Weeds EastCan., 1, 205-206, 1995. The treatment of glyphosate-resistant maize orglyphosate-resistant soya with mixtures of glyphosate and atrazine,metolachlor or dimethenamide is described in Abstr. Meet. Weed Sci. Soc.Am. 37, 87, 1997, Res. Rep. North Cent. Weed Sci. Soc., 52, 426-427,1995 and Res. Rep. North Cent. Weed Sci. Soc., 52, 266-267, 1995.

The active ingredient combination used according to the inventioncontains glufosinate or glyphosate and at least one of the otherherbicides in any ratio of the mixture, normally with an excess of onecomponent over the other. Preferred ratios between glufosinate orglyphosate and the components in the mixture lies between 1:100 and1:0.001.

A preferred process according to the present invention is characterisedin that a herbicidally effective amount of a composition containing, inaddition to the usual inert formulation assistants, glufosinate and asynergistic amount of at least one further herbicide selected from thegroup comprising prosulfuron, primisulfuron, dicamba, pyridate,dimethenamide, metolachlor and its S-enantiomer, fluometuron,propaquizafop, atrazine, ametryn, terbutylazine, simazine, prometryn, aswell as the compounds of formulae

is allowed to take effect on the cultivated plant or its habitat.

Mixtures that have proved to be especially effective when the usefulplant cultivation relates to maize, which is resistant to glufosinateand/or glyphosate, are combinations of glufosinate or glyphosate with asynergistic amount of at least one further herbicide selected from thegroup comprising prosulfuron, primisulfuron, dicamba, pyridate,dimethenamide as well as its S-enantiomer, metolachlor as well as itsS-enantiomer, atrazine, NOA-402989, ametryn, terbutylazine, simazine,prometryn, as well as the compounds of formulae

or combinations of glufosinate with a synergistic amount of at least onefurther herbicide selected from the group comprising prosulfuron,primisulfuron, dicamba, pyridate, dimethenamide, metolachlor as well asits S-enantiomer, atrazine, ametryn, terbutylazine, simazine, prometryn,as well as the compounds of formulae

When the useful plant cultivation relates to soya, which is resistant toglufosinate and/or glyphosate, it is preferable to use a compositionwhich contains glufosinate or glyphosate and a synergistic amount of atleast one further herbicide selected from the group comprisingmetolachlor as well as its S-enantiomer and the compounds of formula

or a composition which contains glufosinate and at least one furtherherbicide selected from the group comprising metolachlor as well as itsS-enantiomer and the compounds of formulae

In cotton cultivations, which are resistant to glufosinate and/orglyphosate, a composition is preferably employed which containsglufosinate or glyphosate and a synergistic amount of fluometuron, orwhich contains glufosinate and a synergistic amount of fluometuron.

In rape or beet cultivations, which are resistant to glufosinate and/orglyphosate, a composition is preferably selected which containsglufosinate or glyphosate and a synergistic amount of propaquizafop, orwhich contains glufosinate and a synergistic amount of propaquizafop.

When the useful plant cultivation concerned is sugar cane, which isresistant to glufosinate and/or glyphosate, it is preferable to use acomposition which contains glufosinate or glyphosate and a synergisticamount of ametryn, or a composition containing glufosinate and asynergistic amount of ametryn.

The amount applied may vary within a wide range, and depends on thenature of the soil, the type of application (pre- or post-emergent; seeddisinfecting; usage in the seed drill; no tillage application etc.), theplant cultivated, the weed to be controlled, the prevalent climaticconditions and other factors determined by the type of application, timeof application and target cultivation. In general, the active ingredientmixture used according to the invention may be used at an applicationrate of 0.3 to 4.0 kg active ingredient mixture per hectare.

In the composition used according to the invention, glufosinate orglyphosate is preferably present in a weight ratio of 1:10 to 1000:1 inrelation to the other herbicide(s).

The herbicidal compositions which contain, in addition to the usualinert formulation assistants, glufosinate and a synergistic amount of atleast one further herbicide selected from the group comprisingprosulfuron, primisulfuron, pyridate, dimethenamide and itsS-enantiomer, the S-enantiomer of metolachlor, fluometuron,propaquizafop, clodinafop, norflurazone, ametryn, terbutylazine,simazine, prometryn, NOA-402989, as well as the compounds of formulae

as well as the herbicidal compositions which contain, in addition to theusual inert formulation assistants, glyphosate and a synergistic amountof at least one further herbicide selected from the group comprisingprosulfuron, primisulfuron, dicamba, pyridate, the S-enantiomer ofdimethenamide, the S-enantiomer of metolachlor, fluometuron,propaquizafop, clodinafop, norflurazone, ametryn, terbutylazine,simazine, prometryn, NOA-402989, as well as the compounds of formulae

are new and form a further object of the present invention.

Both glufosinate and/or glyphosate and the other herbicides may be usedin unchanged form, i.e. as they occur during synthesis, but they arepreferably processed in conventional manner with the assistants whichare customary in formulation technology, such as solvents, solidcarriers or surfactants, e.g. into emulsifiable concentrates, directlysprayable or diluable solutions, spray powders, soluble powders, dustingcompositions, granulates or micro-capsules. The application processessuch as spraying, atomizing, dusting, sprinkling, dispersing or pouringare selected according to the aims strived for and the given conditions,in the same way as for the type of composition.

The formulations, i.e. the compositions, preparations or compositionscontaining the active ingredient glufosinate or glyphosate and the otherherbicides as well as optionally one or several solid or liquidformulating assistants, are produced in a manner known per se, e.g. byintimately mixing and/or grinding the active ingredients with theformulating assistants such as solvents or solid carriers. In addition,surface-active compounds (surfactants) may be used when producing theformulations.

The solvents in question may be: aromatic hydrocarbons, preferablyfractions C₈ to C₁₂, such as xylene mixtures or substitutednaphthalenes, phthalic acid esters such as dibutyl or dioctyl phthalate,aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols andglycols, as well as the ethers and esters thereof, such as ethanol,ethylene glycol, ethylene glycol monomethyl- or -ethyl-ether, ketonessuch as cyclohexanone, strongly polar solvents such asN-methyl-2-pyrrolidone, dimethyl sulphoxide or N,N-dimethylformamide, aswell as optionally epoxidated vegetable oils such as epoxidated coconutoil or soybean oil; or water.

The solid carriers employed e.g. for dusting compositions anddispersible powders are normally natural mineral powders, such ascalcite, talc, kaolin, montmorillonite or attapulgite. To improve thephysical properties of the formulation, highly disperse silicic acid orhighly disperse absorbent polymerisates may also be added. The granular,adsorptive granulate carriers employed may be porous types such aspumice, brick fragments, sepiolite or bentonite, and the non-absorbentcarrier materials are e.g. calcite or sand. Moreover, a number ofpregranulated materials of inorganic or organic nature may also be used,especially dolomite or pulverized plant residue.

Depending on the type of active ingredient to be formulated, thesurface-active compounds may be non-ionic, cationic and/or anionicsurfactants and surfactant mixtures having good emulsifying, dispersingand wetting properties.

Appropriate anionic surfactants may be both so-called water-solublesoaps and water-soluble synthetic surface-active compounds.

Soaps which may be mentioned are the alkali salts, alkaline earth saltsor optionally substituted ammonium salts of higher fatty acids(C₁₀-C₂₂), e.g. the Na or K salts of oleic or stearic acid, or ofnatural fatty acid mixtures, which may be obtained e.g. from coconut oilor tallow oil. Furthermore, the fatty acid methyl-taurine salts may alsobe mentioned.

More frequently however, so-called synthetic surfactants are used,especially fat alcohol sulphonates, fat alcohol sulphates, sulphonatedbenzimidazole derivatives or alkylaryl sulphonates.

The fat alcohol sulphonates or sulphates are normally present as alkalisalts, alkaline earth salts or optionally substituted ammonium salts andhave an alkyl radical with 8 to 22 C-atoms, whereby alkyl also includesthe alkyl moiety of acyl radicals, e.g. the Na or Ca salt of ligninsulphonic acid, of dodecylsulphuric acid ester or of a fat alcoholsulphate mixture produced from natural fatty acids. This also includesthe salts of sulphuric acid esters and sulphonic acids of fatalcohol/ethylene oxide adducts. The sulphonated benzimidazolederivatives preferably contain 2 sulphonic acid groups and one fattyacid radical with 8-22 carbon atoms. Alkylaryl sulphonates are e.g. theNa, Ca or triethanolamine salts of dodecylbenzenesulphonic acid, ofdibutylnaphthalene-sulphonic acid or of a naphthalene-sulphonicacid/formaldehyde condensation product.

The corresponding phosphates such as the salts of the phosphoric acidester of a p-nonyl-phenol-(4-14)-ethylene oxide adduct or phospholipidsmay also be considered.

The non-ionic surfactants may be primarily polyglycol ether derivativesof aliphatic or cyclo-aliphatic alcohols, saturated or unsaturated fattyacids and alkylphenols, which may contain 3 to 30 glycol ether groupsand 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to18 carbon atoms in the alkyl radical of the alkylphenols.

Further appropriate non-ionic surfactants are the water-solublepolyethylene oxide adducts to polypropylene glycol,ethylenediamino-polypropylene glycol and alkyl-polypropylene glycol,containing 20 to 250 ethylene glycol ether groups and 10 to 100propylene glycol ether groups, with 1 to 10 carbon atoms in the alkylchain. The said compounds normally contain 1 to 5 ethylene glycol unitsper propylene glycol unit.

Examples of non-ionic surfactants which may be mentioned are nonylphenolpolyethoxy ethanols, castor oil polyglycol ether,polypropylene-polyethylene oxide adducts, tributylphenoxy-polyethoxyethanol, polyethylene glycol and octylphenoxy-polyethoxy ethanol.

Fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylenesorbitan trioleate, may also be considered.

The cationic surfactants in question are in particular quaternaryammonium salts, which contain as the N-substituents at least one alkylradical with 8 to 22 C-atoms and as further substituents low, optionallyhalogenated alkyl, benzyl or low hydroxyalkyl radicals. The salts arepreferably present as halides, methyl sulphates or ethyl sulphates, e.g.stearyl trimethylammonium chloride orbenzyl-di-(2-chloroethyl)-ethylammonium bromide.

The surfactants which are customary in formulation techniques and whichmay also be used in the compositions according to the invention aredescribed inter alia in “Mc Cutcheon's Detergents and EmulsifiersAnnual” MC Publishing Corp., Ridgewood N.J., 1981, Stache, H.,“Tensid-Taschenbuch”, Carl Hanser Verlag, MunichNienna, 1981 and M. andJ. Ash, “Encyclopedia of Surfactants”, Vol I-III, Chemical PublishingCo., New York, 1980-81.

The herbicide formulations normally contain 0.1 to 99% by weight,especially 0.1 to 95% by weight of active ingredient mixture, 1 to 99.9%by weight of a solid or liquid formulation excipient and 0 to 25% byweight, especially 0.1 to 25% by weight of a surfactant.

While concentrated compositions are usually preferred as a commercialproduct, the final user normally uses diluted compositions.

The compositions may also contain further additives such as stabilizers,e.g. optionally epoxidated plant oils (epoxidated coconut oil, rapeseedoil or soybean oil), defoamers, e.g. silicone oil, preservatives,viscosity regulators, binding compositions, adhesives, as well asfertilizers or other active ingredients.

Preferred formulations are made up in particular as follows:

(%=percent by weight)

Emulsifiable concentrates: active ingredient mixture: 1 to 90%,preferably 5 to 20% surface-active composition: 1 to 30%, preferably 10to 20% liquid carrier: 5 to 94%, preferably 70 to 85% Dusts: activeingredient mixture: 0.1 to 10%, preferably 0.1 to 5% solid carrier: 99.9to 90%, preferably 99.9 to 99% Suspension concentrates: activeingredient mixture: 5 to 75%, preferably 10 to 50% water: 94 to 24%,preferably 88 to 30% surface-active composition: 1 to 40%, preferably 2to 30% Wettable powders: active ingredient mixture: 0.5 to 90%,preferably 1 to 80% surface-active composition: 0.5 to 20%, preferably 1to 15% solid carrier material: 5 to 95%, preferably 15 to 90%Granulates: active ingredient mixture: 0.1 to 30%, preferably 0.1 to 15%solid carrier material: 99.5 to 70%, preferably 97 to 85%

The following examples illustrate the invention further withoutrestricting it.

Formulation Examples for the Active Ingredient Mixtures Used Accordingto the Invention (%=percent by weight)

F1. Emulsion concentrates a) b) c) d) active ingredient mixture 5% 10%25% 50% Ca dodecylbenzene sulphonate 6%  8%  6%  8% castor oilpolyglycol ether 4% —  4%  4% (36 mols EO) octylphenol polyglycol ether—  4% —  2% (7-8 mols EO) cyclohexanone — — 10% 20% arom. hydrocarbonmixture 85%  78% 55% 16% C₉-C₁₂

Emulsions of each desired concentration may be produced from suchconcentrates by dilution with water.

F2. Solutions a) b) c) d) active ingredient mixture  5% 10% 50% 90%1-methoxy-3-(3-methoxy- — 20% 20% — propoxy)-propane polyethylene glycolMW 400 20% 10% — — N-methyl-2-pyrrolidone — — 30% 10% arom. hydrocarbonmixture 75% 60% C₉-C₁₂

The solutions are suitable for application in the form of the smallestdroplets.

F3. Spray powder a) b) c) d) active ingredient mixture 5% 25%  50%  80%Na lignin sulphonate 4% — 3% — Na lauryl sulphate 2% 3% —  4% Nadiisobutyl naphthalene — 6% 5%  6% sulphonate octylphenyl polyglycolether — 1% 2% — (7-8 mols EO) highly disperse silicic acid 1% 3% 5% 10%kaolin 88%  62%  35%  —

The active ingredient is mixed well with the additional materials andground well in an appropriate mill. Spray powders are obtained, whichmay be diluted with water to suspensions of any desired concentration.

F4. Coated granules a) b) c) active ingredient mixture 0.1% 5% 15%highly disperse silicic acid 0.9% 2%  2% inorg. carrier material 99.0%93%  83% (Ø 0.1-1 mm) such as CaCO₃ or SiO₂

The active ingredient is dissolved in methylene chloride, sprayed ontothe carrier and the solvent subsequently evaporated in a vacuum.

F5. Coated granules a) b) c) active ingredient mixture 0.1% 5% 15%polyethylene glycol MW 200 1.0% 2%  3% highly disperse silicic acid 0.9%1%  2% inorg. carrier material 98.0% 92%  80% (Ø 0.1-1 mm) such as CaCO₃or SiO₂

The finely ground active ingredient is evenly applied in a mixer ontothe carrier material which has been moistened with polyethylene glycol.In this way, dust-free coated granules are obtained.

F6. Extrusion granules a) b) c) d) active ingredient mixture 0.1% 3% 5%15% Na lignin sulphonate 1.5% 2% 3%  4% carboxymethyl cellulose 1.4% 2%2%  2% kaolin 97.0% 93%  90%  79%

The active ingredient is mixed with the additives, ground and moistenedwith water. This mixture is extruded and subsequently dried in a currentof air.

F7. Dusting composition a) b) c) active ingredient mixture 0.1%  1%  5%talcum 39.9% 49% 35% kaolin 60.0% 50% 60%

By mixing the active ingredient with the carrier materials and grindingin an appropriate mill, a dusting composition is obtained which is readyfor use.

F8. Suspension concentrates a) b) c) d) active ingredient mixture 3%10%  25%  50%  ethylene glycol 5% 5% 5% 5% nonylphenol polyglycol ether— 1% 2% — (15 mols EO) Na lignin sulphonate 3% 3% 4% 5% carboxymethylcellulose 1% 1% 1% 1% 37% aqueous formaldehyde 0.2%   0.2%   0.2%  0.2%   solution silicone oil emulsion 0.8%   0.8%   0.8%   0.8%   water87%  79%  62%  38% 

The finely ground active ingredient is intimately mixed with theadditives. In this way, a suspension concentrate is obtained, from whichsuspensions of any desired concentration may be prepared by dilutionwith water.

It is often more practical to formulate the active ingredientsindividually and then, shortly prior to placing in the applicator, tobring them together in water in the desired mixture ratio as a “tankmixture”.

BIOLOGICAL EXAMPLES Test Description (Per-Emergent Treatment)

Monocotyledoneous and dicotyledoneous weeds and cultivated plants aresown in small plastic pots in standard soil. Directly after sowing, thetest substances are applied in aqueous suspension (500 l water/ha).Subsequently, the test plants are raised under glass under optimumconditions. Evaluation takes place 3 weeks after application using anine-stage appraisal scale (1=complete damage, 9=no effect). Appraisalmarks of 1 to 4 (especially 1 to 3) indicate good to very good herbicideactivity. Appraisal marks of 6 to 9 (especially 7 to 9) show good tovery good tolerance of cultivated plants.

Test Description (Post-Emergent Treatment)

Monocotyledoneous and dicotyledoneous weeds and cultivated plants areraised under glasshouse conditions in small plastic pots in standardsoil. Application of the test substances takes place at the 3 to 6 leafstage of the test plants. The test substances are applied in aqueoussuspension (500 l water/ha) at application rates of 5 to 5000 g/haactive substance). Evaluation takes place 3 weeks after applicationusing a nine-stage appraisal scale (1=complete damage, 9=no effect).Appraisal marks of 1 to 4 (especially 1 to 3) indicate good to very goodherbicide activity. Appraisal marks of 6 to 9 (especially 7 to 9) showgood to very good tolerance of cultivated plants.

In these tests, the herbicide mixtures used according to the inventionshow good control of the weeds.

1. Process for the control of weeds in cultivations of useful plantswhich are resistant to a phospho-herbicide, characterised in that aherbicidally effective amount of a composition containing, in additionto the usual inert formulation assistants, a phospho-herbicide selectedfrom the group comprising glufosinate and glyphosate, a synergisticamount of at least one further herbicide selected from the groupcomprising prosulfuron, primisulfuron, dicamba, pyridate, dimethenamideand its S-enantiomer, metolachlor and its S-enantiomer, fluometuron,propaquizafop, atrazine, clodinafop, norflurazone, ametryn,terbutylazine, simazine, prometryn, NOA-402989, as well as the compoundsof formulae

is allowed to take effect on the cultivated plant or its habitat, withthe provision that compositions containing glufosinate and metolachlor,glufosinate and atrazine, glufosinate and metolachlor and atrazine, aswell as glufosinate and atrazine and dicamba are not used inglufosinate-resistant maize, and further that compositions containingglyphosate and atrazine are not used in glyphosate-resistant maize, andcompositions containing glyphosate and metolachlor or glyphosate anddimethenamide are not used in glyphosate-resistant soya.
 2. Processaccording to claim 1 for the control of weeds in cultivations of usefulplants which are resistant to the herbicide glufosinate, characterisedin that a herbicidally effective amount of a composition containing, inaddition to the usual inert formulation assistants, glufosinate and asynergistic amount of at least one further herbicide selected from thegroup comprising prosulfuron, primisulfuron, dicamba, pyridate,dimethenamide, metolachlor and its S-enantiomer, fluometuron,propaquizafop, atrazine, ametryn, terbutylazine, simazine, prometryn, aswell as the compounds of formulae

is allowed to take effect on the cultivated plant or its habitat. 3.Process according to claim 1, characterised in that the useful plantbeing cultivated is maize which is resistant to glufosinate and/orglyphosate, and the composition contains glufosinate or glyphosate and asynergistic amount of at least one further herbicide selected from thegroup comprising prosulfuron, primisulfuron, dicamba, pyridate,dimethenamide as well as its S-enantiomer, metolachlor as well as itsS-enantiomer, atrazine, NOA-402989, ametryn, terbutylazine, simazine,prometryn, as well as the compounds of formulae


4. Process according to claim 3, characterised in that the useful plantbeing cultivated is maize which is resistant to glufosinate, and thecomposition contains glufosinate and a synergistic amount of at leastone further herbicide selected from the group comprising prosulfuron,primisulfuron, dicamba, pyridate, dimethenamide, metolachlor as well asits S-enantiomer, atrazine, ametryn, terbutylazine, simazine, prometryn,as well as the compounds of formulae


5. Process according to claim 1, characterised in that the useful plantbeing cultivated is soya which is resistant to glufosinate and/orglyphosate, and the composition contains glufosinate or glyphosate and asynergistic amount of at least one further herbicide selected from thegroup comprising metolachlor as well as its S-enantiomer and thecompounds of formula


6. Process according to claim 5, characterised in that the useful plantbeing cultivated is soya which is resistant to glufosinate, and thecomposition contains glufosinate and a synergistic amount of at leastone further herbicide selected from the group comprising metolachlor aswell as its S-enantiomer and the compounds of formulae


7. Process according to claim 1, characterised in that the useful plantbeing cultivated is cotton which is resistant to glufosinate and/orglyphosate, and the composition contains glufosinate or glyphosate and asynergistic amount of fluometuron.
 8. Process according to claim 7,characterised in that the useful plant being cultivated is cotton whichis resistant to glufosinate, and the composition contains glufosinateand a synergistic amount of fluometuron.
 9. Process according to claim1, characterised in that the useful plant being cultivated is rape orbeet which are resistant to glufosinate and/or glyphosate, and thecomposition contains glufosinate or glyphosate and a synergistic amountof propaquizafop.
 10. Process according to claim 9, characterised inthat the useful plant being cultivated is rape or beet which areresistant to glufosinate, and the composition contains glufosinate and asynergistic amount of propaquizafop.
 11. Process according to claim 1,characterised in that the useful plant being cultivated is sugar canewhich is resistant to glufosinate and/or glyphosate, and the compositioncontains glufosinate or glyphosate and a synergistic amount of ametryn.12. Process according to claim 1, characterised in that the useful plantbeing cultivated is sugar cane which is resistant to glufosinate, andthe composition contains glufosinate and a synergistic amount ofametryn.
 13. Process according to claim 1, characterised in that theuseful plant cultivations are treated with the said composition atapplication rates corresponding to 0.3 to 4.0 kg total active ingredientper hectare.
 14. Herbicidal composition for use in the process accordingto claim 1, characterised in that it contains a herbicidally effectiveamount of a composition containing, in addition to the usual inertformulation assistants, a phospho-herbicide selected from the groupcomprising glufosinate and glyphosate, a synergistic amount of at leastone further herbicide selected from the group comprising prosulfuron,primisulfuron, dicamba, pyridate, dimethenamide and its S-enantiomer,metolachlor and its S-enantiomer, fluometuron, propaquizafop, atrazine,clodinafop, norflurazone, ametryn, terbutylazine, simazine, prometryn,NOA-402989, as well as the compounds of formulae

with the provision that compositions containing glufosinate andmetolachlor, glufosinate and atrazine, glufosinate and metolachlor andatrazine, as well as glufosinate and atrazine and dicamba are not usedin glufosinate-resistant maize, and further that compositions containingglyphosate and atrazine are not used in glyphosate-resistant maize, andcompositions containing glyphosate and metolachlor or glyphosate anddimethenamide are not used in glyphosate-resistant soya.
 15. Herbicidalcomposition, characterised in that it contains, in addition to the usualinert formulation assistants, glufosinate and a synergistic amount of atleast one further herbicide selected from the group comprisingprosulfuron, primisulfuron, pyridate, dimethenamide and itsS-enantiomer, the S-enantiomer of metolachlor, fluometuron,propaquizafop, clodinafop, norflurazone, ametryn, terbutylazine,simazine, prometryn, NOA-402989, as well as the compounds of formulae


16. Herbicidal composition, characterised in that it contains, inaddition to the usual inert formulation assistants, glyphosate and asynergistic amount of at least one further herbicide selected from thegroup comprising prosulfuron, primisulfuron, dicamba, pyridate, theS-enantiomer of dimethenamide, the S-enantiomer of metolachlor,fluometuron, propaquizafop, clodinafop, norflurazone, ametryn,terbutylazine, simazine, prometryn, NOA-402989, as well as the compoundsof formulae